Achieving High Performance Metal–Organic Framework Materials through Pore Engineering

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(17), P. 3362 - 3376

Published: Aug. 17, 2021

Achieving high performance functional materials has been a long-term goal for scientists and engineers that can significantly promote science technology development thus benefit our society human beings. As well-known porous materials, metal-organic frameworks (MOFs) are crystalline open made up of molecular building blocks linked by strong coordination bonds, affording pore space storing trapping guest molecules. In terms porosity, MOFs outperform traditional including zeolites activated carbon, showing exceptional porosity with internal surface area to thousands square meters per gram sample periodic sizes ranging from sub-nanometer nanometers. Numerous have synthesized potential applications gaseous fuels separating intractable industrial gas mixtures, sensing physical chemical stimulus, transmitting protons conduction. Compared distinguished their capability adjustment interior modification through engineering, which them preeminent platform exploring performance.Rational combinations rigid units different geometry multibranched organic linkers provided diverse structures, spherical cylindrical, slit, tubular ones isolating or interconnecting in directions, be optimized high-capacity storage. Based on the isoreticular principle approach MOF chemistry, performed exquisite precision, making suitable address industrially important separation. The large cavities readily available encapsulation species, resulting novel composite various functions.In this Account, we summarize recent research progress engineering achieve high-performance materials. We able tune optimize immobilize specific sites, incorporate species into target hydrogen storage, methane light-hydrocarbon purification, proton conduction, especially separations acetylene removal ethylene propylene purification. By chemistry endows multiple functionalities, endeavors brought about customization corresponding application scenarios.

Language: Английский

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Fine pore engineering in a series of isoreticular metal-organic frameworks for efficient C2H2/CO2 separation

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Jan. 11, 2022

The separation of C2H2/CO2 is not only industrially important for acetylene purification but also scientifically challenging owing to their high similarities in physical properties and molecular sizes. Ultramicroporous metal-organic frameworks (MOFs) can exhibit a pore confinement effect differentiate gas molecules similar size. Herein, we report the fine-tuning sizes sub-nanometer scale on series isoreticular MOFs that realize highly efficient separation. subtle structural differences lead remarkable adsorption performances enhancement. Among four MOF analogs, by integrating appropriate size specific binding sites, [Cu(dps)2(SiF6)] (SIFSIX-dps-Cu, SIFSIX = SiF62-, dps 4.4'-dipyridylsulfide, termed as NCU-100) exhibits highest C2H2 uptake capacity selectivity. At room temperature, space SIFSIX-dps-Cu significantly inhibits CO2 takes up large amount (4.57 mmol g-1), resulting IAST selectivity 1787 multiple host-guest interactions both inter- intralayer cavities are further revealed dispersion-corrected density functional theory grand canonical Monte Carlo simulations. Dynamic breakthrough experiments show clean with working 2.48 g-1.

Language: Английский

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Benchmark C₂H₂/CO₂Separation in an Ultra‐Microporous Metal–Organic Framework via Copper(I)‐Alkynyl Chemistry

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(29), P. 15995 - 16002

Published: May 12, 2021

Abstract Separation of acetylene from carbon dioxide remains a daunting challenge because their very similar molecular sizes and physical properties. We herein report the first example using copper(I)‐alkynyl chemistry within an ultra‐microporous MOF (Cu I @UiO‐66‐(COOH) 2 ) to achieve ultrahigh C H /CO separation selectivity. The anchored Cu ions on pore surfaces can specifically strongly interact with molecule through π‐complexation thus rapidly adsorb large amount at low‐pressure region, while effectively reduce CO uptake due small sizes. This material exhibits record high selectivity 185 ambient conditions, significantly higher than previous benchmark ZJU‐74a (36.5) ATC‐Cu (53.6). Theoretical calculations reveal that unique between mainly contributes ultra‐strong binding affinity exceptional performance was evidenced by breakthrough experiments for gas mixtures. work suggests new perspective functionalizing MOFs highly selective over .

Language: Английский

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Visible-light-driven solvent-free photocatalytic CO2 reduction to CO by Co-MOF/Cu2O heterojunction with superior selectivity

Chemical Engineering Journal, Journal Year: 2022, Volume and Issue: 438, P. 135622 - 135622

Published: March 7, 2022

Language: Английский

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Fluorinated metal–organic frameworks for gas separation

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(17), P. 7427 - 7508

Published: Jan. 1, 2022

Fluorinated metal-organic frameworks (F-MOFs) as fast-growing porous materials have revolutionized the field of gas separation due to their tunable pore apertures, appealing chemical features, and excellent stability. A deep understanding structure-performance relationships is critical for synthesis development new F-MOFs. This review has focused on several strategies precise design F-MOFs with structures tuned specific purposes. First, basic principles concepts well structure, modification structure property are studied. Then, applications in adsorption membrane discussed. detailed account capabilities various gases governing provided. In addition, exceptional characteristics highly stable engineered size put into perspective fabricate selective membranes separation. Systematic analysis position revealed that benchmark most challenging separations. The outlook future directions science engineering challenges highlighted tackle issues overcoming trade-off between capacity/permeability selectivity a serious move towards industrialization.

Language: Английский

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Review of technological progress in carbon dioxide capture, storage, and utilization

Gas Science and Engineering, Journal Year: 2023, Volume and Issue: 117, P. 205070 - 205070

Published: July 13, 2023

Language: Английский

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Dense Packing of Acetylene in a Stable and Low‐Cost Metal–Organic Framework for Efficient C₂H₂/CO₂Separation

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(47), P. 25068 - 25074

Published: Sept. 16, 2021

Porous materials for C2 H2 /CO2 separation mostly suffer from high regeneration energy, poor stability, or cost that largely dampen their industrial implementation. A desired adsorbent should have an optimal balance between excellent performance, and low cost. We herein report a stable, low-cost, easily scaled-up aluminum MOF (CAU-10-H) highly efficient separation. The suitable pore confinement in CAU-10-H can not only provide multipoint binding interactions with but also enable the dense packing of inside pores. This material exhibits one highest storage densities 392 g L-1 selective adsorption over CO2 at ambient conditions, achieved by enthalpy (27 kJ mol-1 ). Breakthrough experiments confirm its exceptional performance mixtures, affording both large uptake 3.3 mmol g-1 factor 3.4. achieves benchmark

Language: Английский

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Advances in adsorptive separation of benzene and cyclohexane by metal-organic framework adsorbents

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 437, P. 213852 - 213852

Published: March 6, 2021

Language: Английский

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Optimal Pore Chemistry in an Ultramicroporous Metal–Organic Framework for Benchmark Inverse CO₂/C₂H₂ Separation

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(31), P. 17198 - 17204

Published: May 27, 2021

Abstract Isolation of CO 2 from acetylene (C H ) via ‐selective sorbents is an energy‐efficient technology for C purification, but a strategic challenge due to their similar physicochemical properties. There still no specific methodology constructing that preferentially trap over . We report effective strategy construct optimal pore chemistry in Ce IV ‐based ultramicroporous metal–organic framework ‐MIL‐140‐4F, based on charge‐transfer effects, efficient inverse /C separation. The ligand‐to‐metal cluster charge transfer facilitated by with low‐lying unoccupied 4f orbitals and electron‐withdrawing F atoms functionalized tetrafluoroterephthalate, affording perfect environment match exceptional uptake (151.7 cm 3 −3 along remarkable separation selectivities (above 40) set new benchmark separation, which verified simulated experimental breakthrough experiments. unique recognition mechanism further unveiled situ powder X‐ray diffraction experiments, Fourier‐transform infrared spectroscopy measurements, molecular calculations.

Language: Английский

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Robust and Radiation-Resistant Hofmann-Type Metal–Organic Frameworks for Record Xenon/Krypton Separation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(7), P. 3200 - 3209

Published: Feb. 9, 2022

The discovery of high-performance adsorbents for highly efficient separation xenon from krypton is an important but challenging task in the chemical industry due to their similar size and inert spherical nature. Herein, we report two robust radiation-resistant Hofmann-type MOFs, Co(pyz)[Ni(CN)4] Co(pyz)[Pd(CN)4] (termed as ZJU-74a-Ni ZJU-74a-Pd), featuring oppositely adjacent open metal sites perfect pore sizes (4.1 3.8 Å) comparable kinetic diameter (4.047 Å), affording benchmark binding affinity polarizable Xe gas. These materials thus exhibit both record-high uptake capacities (89.3 98.4 cm3 cm-3 at 296 K 0.2 bar) Xe/Kr selectivities (74.1 103.4) ambient conditions, all which are highest among state-of-the-art reported so far. locations molecules within have been visualized by single-crystal X-ray diffraction studies, centers combined with right aperture can construct a unique sandwich-like site offer unprecedented ultrastrong Ni2+-Xe-Ni2+ interactions xenon, leading record capture capacity selectivity. excellent ZJU-74a-Pd was verified breakthrough experiments gas mixtures, providing unprecedentedly high (4.63 mmol cm-3) productivity (214 g-1).

Language: Английский

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